EP0618896B1 - Procede d'isomerisation - Google Patents

Procede d'isomerisation Download PDF

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Publication number
EP0618896B1
EP0618896B1 EP92924842A EP92924842A EP0618896B1 EP 0618896 B1 EP0618896 B1 EP 0618896B1 EP 92924842 A EP92924842 A EP 92924842A EP 92924842 A EP92924842 A EP 92924842A EP 0618896 B1 EP0618896 B1 EP 0618896B1
Authority
EP
European Patent Office
Prior art keywords
isomer
epimer
enantiomer
cyanide
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92924842A
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German (de)
English (en)
Other versions
EP0618896A1 (fr
Inventor
Ernest Stephen Cleugh
David John Milner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Ltd
Original Assignee
Zeneca Ltd
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Filing date
Publication date
Application filed by Zeneca Ltd filed Critical Zeneca Ltd
Publication of EP0618896A1 publication Critical patent/EP0618896A1/fr
Application granted granted Critical
Publication of EP0618896B1 publication Critical patent/EP0618896B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C255/39—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups with hydroxy groups esterified by derivatives of 2,2-dimethylcyclopropane carboxylic acids, e.g. of chrysanthemumic acids

Definitions

  • This invention relates to a process for converting a first isomer into a second isomer wherein the first and second isomers are epimers of the same compound.
  • the present invention provides a process for obtaining an isomer of a compound of general formula R-CH(CN)-R' (I) wherein R is an ester group linked through the ether oxygen to the carbon atom bearing the cyano group and R' is an optionally substituted aryl or heteroaryl group provided that at least one of R and R' comprises at least one resolved chiral centre which is stable under the conditions of the process, or a racemic modification comprising the isomer and its enantiomer, which comprises the step of treating the epimer of the isomer, or the racemate comprising the epimer and the enantiomer of the epimer, in solution or in slurry in a monohydric lower alkanol containing up to six carbon atoms containing, within the limits of miscibility, water in an amount of less than 20% by volume, in which the epimer or the racemate is partially soluble, with a source of cyanide ions, in the absence of a base, the isomer, or the racemic modification comprising
  • the process of the invention provides a means to obtain the isomer from its epimer where the epimer has been obtained by a production process in admixture with the isomer, and similarly it provides a means to obtain the racemic modification comprising the isomer and its enantiomer from the racemate comprising the epimer and the enantiomer of the epimer where the racemate has been obtained by a production process in admixture with the isomer and its enantiomer.
  • Pyrethroids are usually obtained by esterification processes which yield mixtures of isomers. It is known that some isomers have a greater insecticidal effect than others, and this has led to the development of techniques to separate the more active isomers, and to convert the less active isomers into the more active. Such processes have been described in for example UK patent no. 1582594, European patent no. 107296 and US patent no. 4997970, and are all characterised by the use of a base.
  • the base not only promotes the desired isomerisation by way of proton removal leading to epimerisation at the carbon atom bearing the cyano group but also, unfortunately, can catalyse the decomposition of the esters, leading to lowered yields of the desired product.
  • deltamethrin S- ⁇ -cyano-3-phenoxybenzyl 1R,3R-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate
  • acrinathrin S- ⁇ -cyano-3-phenoxybenzyl Z-1R,3S-3[2-(2,2,2-trifluoro-1-trifluoromethylethoxycarbonyl)vinyl]-2,2-dimethylcyclopropane carboxylate
  • S-fenvalerate S- ⁇ -cyano-3-phenoxybenzyl S-2-(4-chlorophenyl)-3-methylbutyrate
  • lambda-cyhalothrin racemic combination of S- ⁇ -cyano-3-phenoxybenzyl 1R,3R-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-
  • the invention process can be used to obtain deltamethrin, acrinathrin, S-fenvalerate and lambda-cyhalothrin from precursors products in which the desired isomer or racemate is admixed with its epimer or epimer racemate without the danger of loss of yield through base catalysed decomposition.
  • the process appears to operate on a reduced cycle time indicating that the use of cyanide mediated isomerisation offers an unexpected but significant economic advantage in comparison with the known base-catalysed epimerisation processes.
  • Examples of monohydric lower alkanols containing up to six carbon atoms used as solvents or diluents are isopropanol, isobutanol and t -butanol, or mixtures thereof.
  • a proportion of water may be present, within the limits of miscibility, but this is usually less than 20% by volume.
  • the solvent is a branched lower alkanol such as isopropanol containing from 2 to 15% by volume of water.
  • the source of cyanide ions may be an alkali or alkaline earth cyanide, or a quaternary ammonium cyanide.
  • Sodium cyanide and potassium cyanide are particularly preferred. It may be used in solid form, in which case any residual material at the conclusion of the process must be separated from the solid product by selective solubility, either by washing with water to dissolve the cyanide, or by extraction with an organic solvent to dissolve the product.
  • the cyanide may be in the form of an aqueous solution, which if used in excess may give rise to a two-phase system when certain solvents are used, in which case the process may be facilitated by the use of phase-transfer catalysts, such as the aforementioned quaternary ammonium cyanide.
  • the cyanide is present in an amount of from 0.5 to 15 mole % of the epimer.
  • the solvent or diluent is preferably wet isopropanol containing from 2 to 15% water by volume
  • the source of cyanide ions is preferably sodium cyanide present in an amount of from 0.5 to 15 mole % of the epimer and its enantiomer.
  • One convenient technique for isolating the product is to discharge the contents of the reaction vessel into an excess of dilute aqueous acid, such as sulphuric acid, or preferably a dilute aqueous solution of an alkali metal hypochlorite.
  • This technique can be used with reaction mixtures involving cyanide in either solid or solution form, and permits recovery of the product by either filtration or solvent extraction.
  • the process is conducted in vessels in which the temperature may be controlled by external heating or cooling.
  • the rate of deposition of the crystalline product is enhanced by reducing the solubility of the product by operating at lower temperatures, and by agitation of the vessel contents so as to provide thorough mixing.
  • the period over which the process is conducted will depend upon the rate at which the product is formed, but is unlikely to be less than one hour or more than 60 hours.
  • the precise conditions required will vary according to the particular product, but in general the process may be operated at a temperature in the range -10°C to 20°C for a period of from 15 to 45 hours.
  • the process can be conducted merely by adding the cyanide to a solution of the epimer and agitating the mixture at the relevant temperature for a period, it is often helful, especially for products having lower melting points or relatively higher solubility, to add a quantity of the product in solid crystalline form to the mixture so as to provide a crystalline surface on which further product can crystallise.
  • the amount of added crystalline product is not critical provided that it is sufficient to provide a saturated solution with some remaining in the undissolved state at the particular operating temperature.
  • lambda-cyhalothrin is a racemic product consisting of the isomer S- ⁇ -cyano-3-phenoxybenzyl 1R,3R-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-cyclopropane carboxylate and its enantiomer.
  • Lambda-cyhalothin is obtained from cyhalothrin, which is produced as a mixture of four isomers in approximately equal amounts, the two isomers constituting lambda-cyhalothrin and the epimers of these two isomers, that is R- ⁇ -cyano-3-phenoxybenzyl 1R,3R-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-cyclopropane carboxylate and its enantiomer, respectively.
  • these two pairs of isomers are referred to hereinafter as "Isomer Pair I" (lambda-cyhalothrin) and "Isomer Pair II".
  • Cyhalothrin (105g), wet isopropanol containing 2.7 or 8.0% w/w water (270g), sodium cyanide (6.5g), and crystalline lambda-cyhalothrin are charged to a 1-litre glass vessel fitted with an twin turbine glass agitator and a cooling jacket and maintained at a temperature of -5°C by circulation of a cooled mixture of water and ethylene glycol with agitation for a period of 24 hours after which the ratio of Isomer Pair I/Isomer Pair II was determined by a gas chromatographic technique. The agitation is continued for a further 24 hours an a second determination of the I/II ratio made.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Saccharide Compounds (AREA)
  • Steroid Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Lubricants (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Claims (10)

  1. Procédé d'obtention d'un isomère d'un composé de formule générale

            R-CH(CN)-R'     (I)

    dans laquelle R est un groupe ester lié par l'intermédiaire d'oxygène d'éther à l'atome de carbone portant le groupe cyano et R' est un groupe aryle ou hétéroaryle facultativement substitué, sous réserve que l'un au moins des groupes R et R' comprenne au moins un centre de chiralité dédoublé qui soit stable dans les conditions du procédé, ou d'une forme racémique comprenant l'isomère et son énantiomère, procédé qui comprend l'étape de traitement de l'épimère de l'isomère, ou du racémate comprenant l'épimère et l'énantiomère de l'épimère, en solution ou en suspension dans un alcanol inférieur monohydroxylique ayant jusqu'à 6 atomes de carbone, contenant, dans les limites de miscibilité, de l'eau en une quantité inférieure à 20 % en volume, dans laquelle l'épimère ou le racémate est partiellement soluble, avec une source d'ions cyanure, en l'absence d'une base, l'isomère, ou la forme racémique comprenant l'isomère et son énantiomère, étant moins soluble dans le solvant ou le diluant que, respectivement, l'épimère de l'isomère ou le racémate comprenant l'épimère de l'isomère et l'énantiomère de l'épimère.
  2. Procédé suivant la revendication 1, dans lequel l'épimère a été obtenu par un procédé de production en mélange avec l'isomère, ou dans lequel le racémate a été obtenu par un procédé de production en mélange avec l'isomère et son énantiomère.
  3. Procédé suivant la revendication 1 ou la revendication 2, dans lequel le composé de formule I est un pyréthroïde doué d'activité insecticide.
  4. Procédé suivant la revendication 3, dans lequel le pyréthroïde est choisi entre la deltaméthrine, l'acrinathrine, le S-fenvalérate et la lambda-cyhalothrine.
  5. Procédé suivant la revendication 1, dans lequel le cyanure est un cyanure de métal alcalin.
  6. Procédé suivant la revendication 5, dans lequel le cyanure est utilisé sous la forme solide.
  7. Procédé suivant la revendication 5, dans lequel le cyanure est utilisé sous la forme d'une solution aqueuse en présence d'un catalyseur de transfert de phase.
  8. Procédé suivant la revendication 1, mis en oeuvre à une température comprise dans la plage de -10°C à 20°C.
  9. Procédé suivant la revendication 3, dans lequel le solvant ou le diluant est de l'isopropanol mouillé qui contient 2 à 15 % en volume d'eau.
  10. Procédé suivant la revendication 2, dans lequel le composé de formule I est la lambda-cyhalothrine et le solvant ou diluant est de l'isopropanol mouillé contenant 2 à 15 % en volume d'eau, et la source d'ions cyanure est le cyanure de sodium présent en une quantité de 0,5 à 15 moles % de l'épimère et de son énantiomère.
EP92924842A 1991-12-24 1992-12-15 Procede d'isomerisation Expired - Lifetime EP0618896B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB919127355A GB9127355D0 (en) 1991-12-24 1991-12-24 Isomerisation process
GB9127355 1991-12-24
PCT/GB1992/002323 WO1993013053A2 (fr) 1991-12-24 1992-12-15 Procede d'isomerisation

Publications (2)

Publication Number Publication Date
EP0618896A1 EP0618896A1 (fr) 1994-10-12
EP0618896B1 true EP0618896B1 (fr) 1996-09-11

Family

ID=10706802

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92924842A Expired - Lifetime EP0618896B1 (fr) 1991-12-24 1992-12-15 Procede d'isomerisation

Country Status (26)

Country Link
US (1) US5334744A (fr)
EP (1) EP0618896B1 (fr)
JP (1) JP3490083B2 (fr)
KR (1) KR100249399B1 (fr)
AT (1) ATE142617T1 (fr)
AU (1) AU679168B2 (fr)
BG (1) BG61446B1 (fr)
BR (1) BR9206983A (fr)
CA (1) CA2126180C (fr)
CZ (1) CZ287245B6 (fr)
DE (1) DE69213761T2 (fr)
DK (1) DK0618896T3 (fr)
ES (1) ES2091497T3 (fr)
FI (1) FI114465B (fr)
GB (2) GB9127355D0 (fr)
GR (1) GR3021271T3 (fr)
HU (1) HU214673B (fr)
NO (1) NO300678B1 (fr)
NZ (1) NZ246081A (fr)
RO (1) RO114125B1 (fr)
RU (1) RU2129536C1 (fr)
SK (1) SK281750B6 (fr)
TW (1) TW318827B (fr)
UA (1) UA39862C2 (fr)
WO (1) WO1993013053A2 (fr)
ZA (1) ZA929971B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0229803D0 (en) 2002-12-20 2003-01-29 Syngenta Ltd Chemical process
KR101595453B1 (ko) 2014-06-30 2016-02-19 대한민국 보안등의 고정식 차광기구
KR101595456B1 (ko) 2014-06-30 2016-02-19 대한민국 보안등의 가변식 차광기구
CN107673996A (zh) * 2017-09-28 2018-02-09 浙江工业大学 一种低活性氰戊菊酯异构体向高活性氰戊菊酯异构体转化的方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1062334A (en) * 1963-09-19 1967-03-22 Merck & Co Inc Racemization of compounds containing an asymmetric quaternary carbon atom
FR2375161A1 (fr) * 1976-04-23 1978-07-21 Roussel Uclaf Procede de transformation d'un ester d'acide chiral d'alcool secondaire a-cyane optiquement actif de structure (r) en ester d'acide chiral d'alcool secondaire a-cyane de structure (s)
FR2348901A1 (fr) * 1976-04-23 1977-11-18 Roussel Uclaf Procede de transformation d'un ester d'acide chiral d'alcool secondaire alpha-cyane optiquement actif en ester d'acide chiral d'alcool secondaire alpha-cyane racemique
GB1599876A (en) * 1977-06-13 1981-10-07 Shell Int Research Conversion of a stereoisomer into its diastereoisomer
CH635563A5 (fr) * 1977-07-07 1983-04-15 Sumitomo Chemical Co Procede pour la preparation d'un alpha-cyano-3-phenoxybenzyle optiquement actif.
CA1215717A (fr) * 1977-09-26 1986-12-23 Samuel B. Soloway Methode de conversion d'un ester stereo-isomerique a sa forme de diastereo-isomere
US4308279A (en) * 1979-06-06 1981-12-29 Fmc Corporation Crystalline, insecticidal pyrethroid
CA1162560A (fr) * 1980-04-23 1984-02-21 Ronald F. Mason Methode de preparation de derives d'esters d'acide cyclopropane-carboxylique
JPS56167654A (en) * 1980-05-28 1981-12-23 Sumitomo Chem Co Ltd Method for obtaining stereoisomeric mixture of more highly active phenylacetic ester derivative
JPS5762298A (en) * 1980-10-01 1982-04-15 Mitsubishi Chem Ind Ltd Preparation of 17alpha-cyanosteroid
EP0050521B1 (fr) * 1980-10-20 1984-11-21 Sumitomo Chemical Company, Limited Préparation d'esters optiquement actifs d'acides isovalériques à activité insecticide
GB2130199A (en) * 1982-10-11 1984-05-31 Ici Plc An enantiomeric pair of cyhalothrin isomers and process for the preparation thereof
EP0107296B1 (fr) * 1982-10-18 1987-07-15 Imperial Chemical Industries Plc Produit insecticide et sa préparation
CA1206483A (fr) * 1982-11-11 1986-06-24 Johannes Van Berkel Preparation de derives d'esters d'acide cyclopropane-carboxylique
DE3401483A1 (de) * 1984-01-18 1985-07-25 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung bestimmter enantiomerenpaare von permethrinsaeure-(alpha)-cyano-3-phenoxy-4-fluor-benzyl-ester
GB8418331D0 (en) * 1984-07-18 1984-08-22 Ici Plc Insecticidal ester
GB8422872D0 (en) * 1984-09-11 1984-10-17 Ici Plc Insecticidal product
US4997970A (en) * 1987-06-15 1991-03-05 Fmc Corporation Conversion of pyrethroid isomers to move active species

Also Published As

Publication number Publication date
GB9225856D0 (en) 1993-02-03
GB9127355D0 (en) 1992-02-19
NO942400D0 (fr) 1994-06-23
CZ287245B6 (cs) 2000-10-11
RO114125B1 (ro) 1999-01-29
TW318827B (fr) 1997-11-01
WO1993013053A3 (fr) 1993-08-05
DE69213761T2 (de) 1997-02-13
FI942989A0 (fi) 1994-06-21
KR100249399B1 (ko) 2000-03-15
GR3021271T3 (en) 1997-01-31
DE69213761D1 (de) 1996-10-17
HU214673B (hu) 1998-04-28
CA2126180A1 (fr) 1993-07-08
BR9206983A (pt) 1995-12-05
BG61446B1 (en) 1997-08-29
NZ246081A (en) 1995-11-27
JPH07502995A (ja) 1995-03-30
SK76094A3 (en) 1995-02-08
NO942400L (fr) 1994-08-11
RU94031154A (ru) 1996-05-27
ES2091497T3 (es) 1996-11-01
HUT71704A (en) 1996-01-29
BG98874A (bg) 1995-03-31
SK281750B6 (sk) 2001-07-10
CA2126180C (fr) 2003-05-06
KR940703805A (ko) 1994-12-12
JP3490083B2 (ja) 2004-01-26
DK0618896T3 (fr) 1997-02-24
CZ153694A3 (en) 1995-02-15
ZA929971B (en) 1993-07-07
AU3093292A (en) 1993-07-28
EP0618896A1 (fr) 1994-10-12
WO1993013053A2 (fr) 1993-07-08
FI114465B (fi) 2004-10-29
UA39862C2 (uk) 2001-07-16
ATE142617T1 (de) 1996-09-15
FI942989A (fi) 1994-06-21
RU2129536C1 (ru) 1999-04-27
US5334744A (en) 1994-08-02
GB2262737A (en) 1993-06-30
AU679168B2 (en) 1997-06-26
NO300678B1 (no) 1997-07-07

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